Color photographic light sensitive materials for a silver dye bleaching process

ABSTRACT

A COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL FOR A SILVER DYE BLEACHING PROCESS COMPRISING A SUPPORT HAVING THEREON A PHOTOGRAPHIC EMULSION LAYER CONTAINING A CYAN DYE REPRESENTED BY THE FOLLOWING GENERAL FORMULA:   C6H5-CO-NH-(3,6-DI(HO3S-),8-HO-NAPHTH-1,7-YLENE)-N=N-   (2,5-DI(CH3-O-)-1,4-PHENYLENE)-N=N-(3,6-DI(HO3S-),1-HO-   NAPHTH-2,8-YLENE)-NH-CO-C6H4-NO2   WHEREIN SAID NITRO GROUP IS AT THE PARA- OR META-POSITION OFTHE BENZOYL NUCLEUS AND METHOD FOR PREPARING SAME IS DISCLOSED.

June 12, 1973 MAKOTO os m ETAL 3,738,839

COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS FOR A SILVER DYE BLEACHING PROCESS Filed Oct. 19, 1970 OPTICAL DENSITY WAVE LENGTH (m ,1)

I NVENTORS MAKOTO YOSHIDA SHINICHI IMAI JUNITI TAMANO BY SW1, M, Z; a w

ATTORNEYS United States Patent O U.S. CI. 96-99 6 Claims ABSTRACT OF THE DISCLOSURE A color photographic light-sensitive material for a silver dye bleaching process comprising a support having thereon a photographic emulsion layer containing a cyan dye represented by the following general formula:

OOHN

OH OOHa wherein said nitro group is at the paraor meta-position of the benzoyl nucleus and method for preparing same is disclosed.

BACKGROUND OF THE INVENTION The present invention is concerned with a color photographic light-sensitive material for a silver dye bleaching process, said light-sensitive material containing a specific cyan dye in the silver halide light-sensitive emulsion layer thereof.

Many of cyan dyes for color photographic light-sensitive materials applicable to silver dye bleaching processes are azo dyes and it is necessary that these azo dyes be bleached in proportion to the silver image formed by development in order to provide a cyan colored positive image. Accordingly, in order that a dye of this nature can be used, the azo group present in the dye must be readily decomposed by reduction in proportion to the amount of silver present so as to permit the dye to be completely bleached. Furthermore, it is necessary that in cases where the dye is to be incorporated into a silver halide emulsion layer, that the dye not diffuse into other emulsion layers and diminish photographic properties such as fog and desensitization. Moreover, the dye must maintain 3,738,839 Patented June 12, 1973 certain properties, such as stability to the severe development, dye bleaching treatment, and silver bleaching treatment in a silver dye bleaching process. In addition, the

dye should have sufficient fastness to light, heat and humidity.

SUMMARY OF THE INVENTION It, therefore, is an object of the present invention to provide color photographic light-sensitive materials containing an excellent novel cyan dye which satisfies the above-mentioned criteria.

Still, it is another object of the present invention to provide dyes which are easily produced and excellent in color and hue.

These and other objects are attained by using a cyan MCFM. \/SOaH CH3 H033 S0311 dye as shown in the following general Formula 1 in a color photographic light-sensitive material for silver dye bleaching process:

OCHa OH NHC O wherein the nitro group may be in the para-position or the meta-position on the benzoyl nucleus.

The cyan dyes used for color photographic light-sensitive materials applicable to the silver dye bleaching process are mainly bisazo dyes. According to a general method for producing those bisazo dyes, 4-nitro2,5-dimethoxyaniline is first diazotized and coupled with l-amino-S- naphthol-3,4-disulfonate derivative to provide a monoazonitro compound. The product so obtained is reduced to give a monoazoamino compound, and this amino compound is diazotized and coupled with a l-amino-S-naphthol-3,4disulfonate derivative to provide the bisazo dye.

The above reaction is usually conducted in 21 aqueous solution. However, since the intermediate products prepared in the above reaction and the dye are easily soluble in water, a large amount of a salt must be added to the reaction system to salt out the final product from the reaction product liquid. Moreover, it is quite difficult to obtain the pure dye by removing salts contained in the dye thus salted out. Hence, in the case of producing a dye which is too easily soluble in water, the production process becomes hampered and the yield of the dye is reduced. The cyan dyes of this invention can be effectively in- This results in higher dye cost as well as the dye remaincorporated in silver halide photographic emulsion without g Unsuitable C0101 Photographic light-Sensitive diminishing the photographic properties thereof. When materials. they are incorporated into a silver halide photographic DETAILED DESCRIPTION THE INVENTION emulsion layer, they can be easily bleached in proportion to the silver image. The cyan dyes of this invention also possess sufiicient fastness to development of chemicals, heat, light and moisture and are thus quite desirable for color photographic light-sensitive material applicable to Therefore, the inventors have investigated dyes which can be produced with a good yield by a simple production process and yet provide dyes which are suitable for purposes of the present invention. The dyes used in this invention have one nitro group at the para-position or the a Silver y bleeehlhg P meta-position of the benzoyl nucleus. The solubility of the The cyan dyes of the present lnventron can not only dye in water is low as compared with that of dye A havbe used in natural color photographic light-sensitive maihg I10 hitfb group and Shown y the following formula! terials for the silver dye bleaching process but also in D A color photographic light-sensitive materials for silver dye @OCHN t n 0on3 OH I noo fiN=N N=N q Hogs SOSH OCH; H035 It Upon comparing the dififusion coefficient of the dyes in bleaching process wherein mono-C0101 lmages and gelatin as a comparison for showing their solubility in wac010T Images are (teSITedter, the diffusion coefiicients of the dyes represented by the r he eoheehtfatlbh 0f the y y 1S detefmlheq y a above-mentioned general Formula I having a nitro group P h y test; In Order to p fl the P p Image at the para-position or the meta-position are 0.02 10 deh $1ty- Aceefdlhgly, the eoheehtratloh necessary can b cm. /sec. in both cases. On the other hand, dye A shown easllyftetefmthed y the Skllled In the art of Photographle above and a dye represented by the general Formula I matellelswherein a nitro group is at the ortho-position have diffu- The y y of the Present lhyel'ltloh are those Shown sion coefficients of 0.12 10 cmP/sec. and 2.2 10 1n the followmg formulae: cm. /sec., respectively. Thus, the diffusion coefficient of The y Portloh Illustrated the dye of this invention is about /6 of that of the dye A and about of that of the ortho-nitro substituted 11 OCH! dye, which illustrates that the dyes of the present invention are weakly soluble in water. Dye A and the ortho- Q nitro substituted dye will be diffused from a gelatin layer H038 503E CH3 and hence are unsuitable as dyes for color photographic light-sensitive materials. The above-mentioned excellent property of the dyes of the present invention resides in Formula 1 the effect of the substituted nitro group and the position of the nitro group. It has not been expected that one nitro group and the position of the nitro group could pro- 0H IlIHCOQNOZ vide such an influence on the solubility of these dyes in water. In addition, the diffusion coefiicient of these dyes in gelatin is obtained by measurin the concentration of the dye diffused in pure gelatin when a gelatin gel containing the dye is brought into contact with pure gelatin for a definite period of time. Calculations are then made according to Ficks law.

OH NHCO As mentioned above, since the dyes of the present 111- l vention have a desirable low solubility in water, they A No2 may be prepared with excellent yield, low cost and can be very profitable as a cyan dye for color photographic Hogs S0311 light-sensitive materials.

Also, as made clear from the accompanying drawing, Thesfi dyes may be prepared b a i h fo ward the y 0f the Present inigention give y excellent color process as described below: all parts are by weight unless and hue as compared with that of an ortho-nitro subotherwise stated a t dd h' t S 1 u e Ye W a 8 SYNTHESIS 1.THE DYE HAVING STRUCTURAL BRIEF DESCRIPTION OF THE DRAWING FORMULA 2 That is to y, in the figure 0f the accompanying drew" (1-1): Synthesis of the diazo component mg, curve 1 stands for the absorption curve of an aqueous solution of a dye of the present invention represented by 198 P liammozs'dlfnethoxy 4 mtrobenzehe Structural Formula 1 shown below, curve 2 stands for we}? duizottzed a ,sushenslon of Strong hydrochlonc the absorption curve of an aqueous solution of a dye of acldflThls dlatoilzed hquld a added to 423 Parts of a the present invention represented by Structural Formula Solunon cpntamtng libenzoylammofs hYdmXYPaPhtha- 2, and curve 3 stands for the absorption curve of an lene-3,6-d1sulfon1c acid make alkallne with sodium caraqueous solution of the ortho-nitro substituted dye which bonate to couphng; The mtroazo dye t Obtalhed is a structural isomer of the dyes of the present invention. was reduced an k e 501mm by sodlhm Sulfide to It has been discovered that the color photographic '0 F the correspondmg ammoazo (tyegwhlch was 1ight sensitive materials produced by using a cyan dye of Isolated (see, Japanese patent publication No. 25,768/

is denoted by A;

Formula 2 this invention are excellent in their reflectivity curve and 1964) 1 2 S th give an ideal cyan color and hue. Therefore, the cyan yn 6515 of the couphng component dyes of the present invention are particularly useful for 40 parts (by volume) of a 30% aqueous sodium hyreflection-type color photogr ph c light-sensitive materialdroxide solution and 400 parts (by volume) of water were added to 93 parts of 1-amino-8-naphthol-3,6-disulfonate. After adding 65 parts of sodium carbonate and 72 parts of m-nitrobenzoyl chloride at 35 C., the resultant mixture was heated to 95 C. for 2 hours. During heating, crystal of sodium carbonate was added to the mixture, whereby the mixture was always maintained in a weak alkaline state. After adding to the mixture 100 parts (by volume) of concentrated hydrochloric acid and 200 parts (by volume) of a saturated aqueous solution of sodium chloride, the product was recovered by filtration and dried. The yield of the product was 96 parts.

(1-3): Synthesis of dye (2) parts of the monoazoamino compound obtained in synthesis (1,-1) were dissolved in 150 parts of an aqueous solution containing 25 parts of sodium hydroxide. Subsequently, 1.5 parts of sodium nitrite in 10 parts (by volume) of water were added to the solution prepared above. After adding to the mixture parts (by volume) of concentrated hydrochloric acid at C., the resultant mixture was stirred for 1 hour.

8 parts of the coupling component obtained in synthesis (1-2) were dissolved in a solution containing 150 parts (by volume) of pyridine in 75 parts (by volume) of water. The above-prepared diazonium liquid was added dropwise to the solution at 0-5 C. After allowing to stand overnight, sodium chloride was added to the solution and the dye produced was redissolved in water followed by repeating the salting out process until all purple impurities disappeared. Thereafter, the dye formed was salted out by sodium acetate and after recovering the crystals formed by filtration, the crystals were washed with ethanol and dried. The yield was 9.5 parts. The maximum absorption wave length of an aqueous solution of the dye was 613 millimicrons.

SYNTHESIS 2.THE DYE OF THE STRUCTURAL The objective dye was produced by repeating the same procedure as Synthesis 1 except that p-nitrobenzoyl chloride was used for the synthesis of the coupling component. The maximum absorption wave length of the aqueous solution of the dye was 620 millimicrons.

A better understanding of the present invention may be obtained from the following examples which are merely intended to be illustrative and not limitative of the present invention. All parts are by weight unless otherwise stated.

EXAMPLE 1 1 part of the cyan die shown by the Structural Formula 2 was dissolved in 100 parts (by volume) of aqueous sodium hydroxide solution. 80 parts (by volume) of the cyan dye solution was mixed with 100 parts of silver bromide emulsion containing about 30 parts/ kg. of silver bromide. The mixture was then applied to a film base.

The light-sensitive film thus obtained was exposed under a step wedge and developed for 10 minutes by a developing liquid having the following composition:

Parts N-methyl-p-aminophenol /2 sulfate 2 Anhydrous sodium sulfite 30 Hydroquinone 8 Sodium carbonate 20 Potassium bromide 4 Water added to make 1 liter.

The photographic film thus developed was washed with water and then fixed for 4 minutes by a solution having the following composition:

Parts Anhydrous sodium thiosulfate 350 Anhydrous sodium sulfite 10 Water added to make 1 liter.

The photographic film was then washed with water, hardened by an aqueous solution of 4% formaldehyde, washed with water again, and then processed for 15 minutes by a dye bleaching bath having the following composition:

Parts Thiourea Potassium bromide 30 Concentrated hydrochloric acid (by volume) 30 2-amino-3-hydroxyphenazine 0.01 Water added to make 1 liter.

By repeating the same procedure as in Example 1, using the cyan dye shown by the structural Formula 1, a clear cyan image having the absorption maximum at 623 millimicrons was obtained. The highlight portion of the color image had been completely bleached and hence the cyan image was suitable as a cyan component image for a multi-color light-sensitive material useful in the silver dye bleaching process.

Although the present invention has been adequately described in the foregoing specification and examples included therein, it is readily apparent that various modifications and changes may be made without departing from the scope thereof.

What is claimed is:

1. A color photographic light-sensitive material for a silver dye bleaching process comprising a support having thereon a photographic emulsion layer containing a cyan dye represented by the following general formula:

wherein said nitro group is at the paraor meta-position of the benzoyl nucleus.

2. The color photographic light-sensitive material of claim 1 wherein said cyan dye is Q-OCHN 0H 00H, on r moo No,

1103s so r1 06H no 9 so a 3. The color photographic light-sensitive material of claim 1 wherein said cyan dye is SOaH OCH; H033 O 4. A method for preparing the color photographic light- 10 sensitive material of claim 1, which comprises: (a) dissolving a cyan dye of the formula:

OGHN 11 OCH; C| H IIIHCO N=N N=N H013 SOzH )CHa HO; OaH

'wherein said nitro group is at the paraor the meta- 20 References Cited position of the benzoyl nucleus in an aqueous alkali UNITED STATES PATENTS metal hydroxide solution. 3,236,643 2/1966 Husek 96-99 b th 1 3,287,132 12/1966 Hunt 96-99 1011 of (a) wlh a Iver hall e 25 3,443,952 5/1969 Anderau 96 99 3,443,953 5/1969 Loetfel 96-99 pp y the mlXlure of to a film e. 3,454,402 7 19 9 A 5 9 5. The method of claim 4 wherein the nitro group of 3,454,401 7/1969 Mory 96-99 the benzoyl nucleus is in the para-position, 3,455,695 7/ 1969 1311161 9699 6. The method of claim 4 wherein the nitro group of 30 J. TRAVIS BROWN, Primary Examiner the benzoyl nucleus is in the meta-position. E. C. KIMLIN, Assistant Examiner 

